WO2002068496A1 - Manufacture of cyclic ester oligomers - Google Patents
Manufacture of cyclic ester oligomers Download PDFInfo
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- WO2002068496A1 WO2002068496A1 PCT/US2002/006398 US0206398W WO02068496A1 WO 2002068496 A1 WO2002068496 A1 WO 2002068496A1 US 0206398 W US0206398 W US 0206398W WO 02068496 A1 WO02068496 A1 WO 02068496A1
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- lpe
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- linear polyester
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- 0 C[N+](*[N+]([O-])O*OC)[O-] Chemical compound C[N+](*[N+]([O-])O*OC)[O-] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/81—Preparation processes using solvents
Definitions
- the field of invention relates to cyclic ester oligomers (CEOs) , and in particular, to CEOs manufactured from linear polyesters or their precursors.
- Cyclic ester oligomers have been known for a long time, see for instance U.S. Patent 2,020,298. They are known to be present in varying, usually small, quatities in many linear polyesters and have been isolated from such linear polyesters. They are often low viscosity liquids, and it has been known for a long time that they may be polymerized to higher molecular weight linear polyesters by ring opening polymerization, see for instance U.S. Patents 5,466,744 and 5,661,214 and refeences cited therein.
- the ester groups within (I) and between molecules of (I), as well as the hydroxyl and carboxyl groups in (I) (the end groups) are, under the proper conditions (usually elevated temperatures and optionally in the presence of esterifi- cation/transesterification catalysts) , in equilibrium with one another.
- This chemistry forms the basis for the melt and solid state polymerizations to form linear polyesters. For instance:
- Equation (4) illustrates one way in which the CEOs can be in equilibrium with the linear polyesters (there are other ways, see below) .
- equation (4) shows a CEO being formed by an esterification, they can also be formed by transesterification.
- the linear polyester molecular weight may also be built up by reactions such as
- esterification/transesterification reactions may be speeded up by the addition of esterifi- cation/transesterification catalysts, although it is important to realize that certain catalysts may favor polymerization, depolymerization, linears and cyclics, or combinations of these.
- This invention includes processes for the production of cyclic ester oligomers, comprising, subjecting a linear polyester to a continuous reactive extraction at a temperature at which said linear polyester is molten and which is sufficient to cause formation of said cyclic ester oligomers, wherein at least some of said linear polyester is converted to one or more cyclic ester oligomers and said extraction is carried out by a fluid which is one or both of a liquid and a gas to separate said cyclic ester oligomers from said linear polyester.
- a fluid which is one or both of a liquid and a gas to separate said cyclic ester oligomers from said linear polyester.
- a continuous reactive extraction herein is meant a process wherein linear polyester ester is continuously converted to CEOs, while simultaneously CEOs are separated (extracted) from the linear polyester from which they were formed.
- a linear polyester LPE
- LPE linear polyester
- Cyclic monomers such as for instance aromatic diacids and/or diols or 1, -cyclohexane dicar- boxylic acid, may be present in the linear polyester.
- the word linear refers to the overall architecture of the polymer molecule, not the architecture of individual repeat units. These linear polyesters may contain (usually small) amount of CEOs which are normally made in the preparation of the LPEs, for example, by melt or solid state polymerization.
- the linear polyester is derived from a combination of one or more diols and one or more dicarboxylic acids, a combination of one or more diols, one or more dicarboxylic acids and one or more hydroxy- acids, or a combination of one or more hydroxyacids .
- molten herein, as applied to a polymer, is meant a polymer which is above its highest glass transition temperature and above its crystalline melting point (if it has a crystalline melting point) , whichever is highest. Glass transition temperature melting points are measured by Differential Scanning Calorimetry on the "pure” linear polyesters (no liquid fluid present) using the procedure of ASTM method D3418. Melting points are taken as the peak of the melting endotherm, while glass transition points are taken as the midpoint of the measured transition.
- the sample for glass transition temperature and melting point is prepared by heating the LPE in the liquid to the process temperature and then cooling the LPE (swollen with liquid) to room temperature. The test is then run on the swollen LPE. If the LPE is significantly swollen, the glass transition temperature and/or melting point (if present) may be significantly lowered from that measured with pure LPE. In this instance the glass transition temperature or the melting of the swollen LPE is the taken for the temperature limitation herein. Note that the glass transition temperature and/or melting point of a linear polyester may vary with molecular weight. It is the melting point and/or glass transition temperature of the linear poly- ester actually being added to the process which is the benchmark to be used herein.
- hydrocarbylene herein is meant a divalent group containing carbon and hydrogen which has two free valencies, each to a different carbon atom.
- alkylene herein is meant a saturated divalent group containing carbon and hydrogen which has two free valencies, each to a different carbon atom.
- arylene herein is meant a divalent group con- taining one or more aromatic rings, having two free valencies to 2 different carbon atoms which are part of aromatic rings. If more than one aromatic ring is present the free valencies may be to carbon atoms on the same or different rings.
- the aromatic rings may be fused as in naphthalene, connected by a covalent bond as in biphenyl, or connected by a covalently bonded group, as in diphenyl ether.
- substituted herein is mean that the group or radical group contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected.
- the substituent groups also do not substantially interfere with the process. Included in the meaning of "substituted” are heteroaromatic rings.
- substituted hydrocarbyl all of the hydrogens may be substituted, as in trifluoromethyl .
- Preferred groups for substitution include (where appropriate) alkyl, aryl, ether, halo, oxo (keto) , ester, etc.
- average degree of polymerization herein is meant the average number of repeat units such as (I) in a polymer chain of an LPE.
- a fluid is used to extract the CEO from the process mixture, especially the mixture containing the LPE.
- This fluid may be a liquid or a gas. If it is a gas, the only requirement is that the gas be inert to the process ingredients under the process temperature. Typical gases may be nitrogen, and argon. Oxidizing gases such as oxygen and oxygen containing gases should normally be avoided to avoid oxidation of the process ingredients especially at the elevated process temperature.
- the CEO preferably has some reasonable solubility in the liquid.
- the CEO (or mixture of CEOs) should have a solubility of at least about 0.1% by weight, more preferably at least about 1.0% by weight and very preferably at least about 2.0% by weight in the liquid at the process temperature.
- Process temperature in this context means the temperature at which the LPE is converted to the CEO(s). The higher the solubility of the CEO in the liquid the more favorable the economics of the process can be, since less liquid is required to extract the CEOs.
- the concentration of CEOs in the liquid may also increase, since, as noted above, as the concentration of the polyester (in both LPE and CEO forms) increases, the equilibrium favors the presence of more LPE in the mixture.
- the optimum solubility or amount of CEO in the liquid during the process may be a compromise between economics of CEO production and the purity of the CEO produced.
- the CEO(s) have a solubility at 50°C in the liquid of only about 20% or less, more preferably about 10% or less and especially preferably 5% or less, of its solubility at the process temperature.
- the solubility of the LPE added to the process in the liquid should preferably be about 5% by weight or less, more preferably about 2% by weight or less, of the solubility of the CEOs in the liquid at the process temperature.
- the CEOs should preferably be more soluble in the liquid than the LPE.
- the liquid chosen is preferably reasonably stable at the process temperature. Its atmospheric boiling point should preferably be above the process temperature, but this is not necessary, since the process can be run at elevated pressure to maintain the liquid in the liquid state. However this often entails added expense.
- Preferable liquids include hydrocarbons such as al- kanes, perfluorocompounds including those containing functional groups such as ether and tertiary amino.
- Preferred hydrocarbons are alkanes, especially n-alkanes such a tetradecane and hexadecane.
- Preferred perfluorocompounds include tertiary amines such as perfluoro (tri- n-butylamine) and perfluoro (tri-n-pentylamine) .
- the desired boiling point of the liquid may determine how many carbon atoms the liquid contains.
- the LPE used may have as its repeat units any units as described above.
- the LPE is derived from a diol and dicarboxylic acid, and the repeat unit for the LPE can be written as
- each R 1 in the LPE is independently hydrocarbylene or substituted hydrocarbylene
- each R 2 in the LPE is independently hydrocarbylene or substituted hydrocarbylene.
- each R 1 is independently arylene or substituted arylene
- specifically preferred groups for R 1 are p-phenylene, m-phenylene, a combination of p-phenylene and m-phenylene, and 2, 6-naphthylene.
- R 1 is p-phenylene.
- each R 2 is independently alkylene or substituted alkylene, and it is more preferred that each R 2 is independently -(CH 2 ) y - (II) wherein y is an integer of 2 to 6, more preferably 2, 3 or 4, or R 2 is - (CH 2 CH 2 ) z OCH 2 CH 2 - (III) wherein z is an integer of 1 to 6 , more preferably 1.
- both (II) and (III) are present.
- Preferred specific polymers include poly (ethylene terephthalate) [this polymer often contains some repeat units derived from diethylene glycol which are formed in the polymer synthesis, and these polymers are included within the definition of poly (ethylene terephthalate)], poly (trimethylene terephthalate), poly (1, 4-butylene terephthalate), poly (ethylene isophthalate-terepthalate) , poly (1,4- butylene adipate-terephthalate) , poly(l,4- butylene/ethylene terephthalate) poly (ethylene 2,6- napthalate) , with poly (ethylene terephthalate), poly (trimethylene terephthalate), and poly (1, 4-butylene terephthalate) being particularly preferred.
- the LPE may be of any molecular weight, but it is preferred that it be of relatively low molecular weight.
- the rate of formation CEOs will presumably depend on the concentration of end groups present in the process. Lower molecular weight polymers have higher end group concentrations and so are preferred.
- the LPE has an average DP of about 3 to about 100, more preferably about 3 to about 50, and especially preferably about 3 to about 10.
- the DP is calculation from the number average molecular weight (Mn) , and the Mn is measured by Gel Permeation Chromatography (GPC) using an appropriate polyester as a calibration standard. If the Mn is very low, freezing point depression can be used instead of GPC to measure the Mn.
- GPC Gel Permeation Chromatography
- the LPE have hydroxyl ends. It is believed that the reactions to form CEO from LPE are faster if the polymer chain has hydroxyl ends.
- the product of the process is a CEO corresponding to the structure of the LPE originally added.
- the CEO obtained would be
- x is an integer of one or more. Usually for the great majority of the CEO recovered x will be 10 or less, and may even be only 1. This depends to a certain extent on what R 1 and R 2 are, and the process conditions used.
- the process may be run quite simply.
- the process may be run neat, that is without a solvent for the LPE, or it may be run with a solvent for the LPE to reduce the viscosity.
- the solvent should be relatively nonvolatile.
- the LPE (and solvent if present) is heated to the process temperature and the gas (fluid) is run through (bubbled through) the LPE (solution) .
- the CEOs from the LPE are volatile enough at the process temperature, they will be stripped (extracted) from the LPE as part of the gas stream.
- the gas stream may be kept hot until the gas reaches the desired collection point for the CEOs, when it may be cooled and the CEOs collected as they condense in the vessel.
- the gas stream may be passed through a liquid, preferably an organic liquid, and the CEOs stripped from the gas stream by the liquid.
- the gas may be reheated and recycled through the process.
- fresh LPE may be added to make up for the material stripped from the LPE as CEOs.
- a catalyst (see below) may be present to accelerate the formation of the CEOs from the LPE.
- a preferred apparatus for the process when a gas is used as the fluid is a so-called melt finisher for polyesters.
- Such apparatuses are known in the art.
- one type of finisher is a horizontal cylindrical reactor with the rotating shaft running horizontally through the axis of the cylinder. Attached axially to the shaft are circular screens which rotate (slowly) with the shaft. There may be one screen in the form a screw. Lower molecular weight polymer is fed to the bottom of one end of the cylinder where the rotating screens pick it up and a thin film of polymer forms on the screen (s) as they rotate.
- Preferred processes to form CEOs may also be run using a liquid as the fluid in the process.
- this liquid should (preferably) have certain properties associated with it.
- the CRE stage of the process be run at the boiling point, preferably the atmospheric boiling point, of the liquid. This allows easy control of the process temperature, and also allows the liquid to be "transported" to a desired point in the process as a gas, where it may be condensed to the liquid state.
- any of the preferred conditions and/or values for the process may be combined with any of the preferred conditions and/or values for that process to form a more preferred process.
- a column 100 with sieve trays 102 and downcomers 101, a supply/collector flask 104 connected thereto by connector 105, and a 2-way adapter 106 connecting the column to a polymer receiving flask 103.
- a first inlet 112 e.g., a nitrogen inlet
- a second inlet 113 e.g., a second nitrogen inlet
- liquid (not shown) is initially provided to supply/collector flask 104 and heated by a suitable heating element (not shown) , which is brought to a boil.
- the boiling liquid then refluxes upwards through connector 105 in the direction of third arrow 109 up though column 100 in the direction of second arrow 108.
- LPE (not shown) is introduced into the top sieve tray 102.
- the liquid in its vapor phase, contacts the LPE, which immediately begins to melt (or the LPE may be added already molten) .
- the molten LPO simultaneously drips down the holes (not shown) in the sieve trays 102 (and sometimes downcomers 101) through the column 100 in the direction of first arrow 107.
- the liquid vapor phase condenses and flows down the column 100 in the direction of first arrow 107 through each sieve tray 102 through downcomers 101 while in contact with the molten LPE. Simultaneously, throughout column 100, the molten LPE de-polymerizes into CEO(s), which is carried away in the solvent condensate flowing down the column 100.
- Connector 105 is positioned such that the returning liquid condensate flows down connector 105 in the direction of fourth arrow 110 back into supply/collector flask 104, whereas the molten LPE falls in the direction of fifth arrow 111 through 2-way adapter 106 into the polymer receiving flask 103. Liquid condensate may also flow into the polymer receiving flask 103.
- the molten LPE collected in polymer receiving flask 103 may be recycled to the top of the column 100.
- a first valve 217 regulates solvent fresh feed 216 to supply/collector flask 204.
- a polymer receiving flask 203 is connected to the column 200 by an 2- way adapter 206, and a second connector 219 and second valve 218 connects a receiving flask 213.
- a first inlet 214 e.g., a nitrogen inlet
- a second inlet 215 e.g., a nitrogen inlet
- the set-up in Figure 2 operates similarly to the set-up in Figure 1.
- Boiling liquid (not shown) in supply/collector flask 204 refluxes up through first connector 205 in the direction of third arrow 209 and up the column 200 in the direction of second arrow 208.
- Solid LPE (not shown) (which may also be added molten) is provided at the top of the column.
- the molten LPE flows down the column 200 through sieve trays 202 (and sometimes downcomers 201) in the direction of first arrow 207.
- the liquid condensate also flows down the column 200 in the direction of first arrow 207.
- second connector 219 is positioned such that the returning liquid condensate flows through second connector 219 in the direction of fourth arrow 210 and into receiving flask 213 (although some returning liquid condensate may still flow through first connector 205 in the direction of fifth arrow 211) .
- the molten LPE flows down through 2-way adapter 206 in the direction of sixth arrow 212 and into polymer receiving flask 203, where it may be recycled back to the top of column 200.
- Liquid condensate may also flow into polymer receiving flask 203.
- Liquid fresh feed 216 may provide additional liquid into supply/collector flask 204, in order to make up for the lack of return of liquid condensate from the column 200, as in the set-up of Figure 1.
- FIG. 4 there is provided a column 400 with sieve trays 402 and downcomers 401, a supply/collector flask 404 connected thereto by a first connector 405.
- a first valve 416 regulates a liquid fresh feed 417 to supply/collector flask 404
- a third valve 420 regulates flow out of supply/collector flask 404 to a second collection flask 415.
- a polymer receiving flask 403 is connected to the column 400 by a 2-way adapter 406, and a second connector 412 and second valve 419 connects a first collection flask 413.
- a first inlet 414 e.g., a nitrogen inlet
- a second inlet 418 regulated by a fourth valve 421.
- the set-up in Figure 4 operates similarly to the set-up in Figures 1-3. Boiling liquid refluxes upwards through first connector 405 in the direction of third arrow 409 up though column 400 in the direction of second arrow 408.
- LPE (not shown) is introduced into the top sieve tray 402.
- the liquid vapor phase condenses and flows down the column 400 in the direction of first arrow 407 through each sieve tray 402 through downcomers 401.
- the molten LPE also drips down the holes (not shown) in the sieve trays 402 (and sometimes through downcomers 401) through the column 400 in the direction of first arrow 407.
- second connector 412 is positioned such that the returning liquid condensate flows through second connector 412 in the direction of fifth arrow 422 and into first collection flask 413.
- First connector 405 is positioned such that any additional returning liquid condensate flows down first connector 405 in the direction of fourth arrow 410 back into supply/collector flask 404, whereas the molten LPE falls through 2-way adapter 406 in the direction of fifth arrow 411 into the polymer receiving flask 403, where it may be recycled back to the top of column 400.
- the contents of supply/collector flask 404 may be removed into second collection flask 415 as regulated by third valve 420 from time to time.
- First phase fresh feed 417 may provide additional liquid into supply/collector flask 404, in order to compensate for such removal.
- My processes differ from the usual extraction in that the material being extracted is continuously being formed from the material from which it is being separated. It is believed that partial or complete con- version of the LPE into CEO(s) is possible in a single pass or with multiple passes through preferred processes of my invention. For example, if any preferred apparatus of Figures 1-4 is employed, a column could be designed to obtain complete conversion by allowing for sufficient hold-up time on the trays and overall residence time in the column. Even assuming that only partially converted molten LPE would still exit the bottom of the column, this exiting LPE can be returned to the top of the column for further conversion.
- At least 25 weight percent, more preferably at least 50 weight percent, especially preferably at least 75 weight percent and very preferably at least 90 weight percent of the original LPE is converted to and isolated as CEO(s) in one or more passes through the process, preferably in one pass through the process.
- the volume ratio of liquid in contact with the LPE in the process is about 10:1 to about 1:10, preferably about 2:1 to about 1:2. "In contact with” in this instance means under conditions in which the CEO can be effectively extracted from the LPE.
- temperatures sufficient to cause such reactions.
- the temperatures employed can be quite varied, and are dependent upon process variables such as the rate of production of the CEOs desired, the particular LPE used and its reactivity and thermal stability, whether a catalyst is present and what its activity enhancement is, etc.
- the temperature is readily determined by things such as the known thermal stabilities of various LPEs, and/or some simple experimentation. Generally speaking this process for many LPEs can be run in the temperature range of about 100°C to about 400°C.
- a catalyst to accelerate the reaction of the LPE to form CEO(s) may optionally be present in my processes, in particular in contact with (for example dissolved in) the LPE. These catalysts are preferably those catalysts which are particularly useful for transesterification.
- the catalysts are added to the LPE in any convenient form, for example dissolved in or mixed with the LPEs and in typical amounts, usually 0.01 to 1.0 weight percent of the original amount of LPE present or the amount of LPE being fed to the process. It is understood that the relative amounts of LPE to catalyst within the process may vary in different parts of the process because the LPE is constantly being converted to CEOs.
- the CEOs which are produced by my processes are useful as monomers for forming polyesters by ring opening polymerizations.
- the relatively low viscosity CEOs may be pumped into a mold and polymerized in the mold to form a final part shape which may be used.
- EXAMPLE 1 Referring to Figure 3, an Oldershaw, perforated bubble plate, distillation column (28 mm inner diameter, 10 plate sections, available from LabGlass, Vineland, New Jersey, as item #LG-5621-122) (300) having downcomers (301) and sieve trays (302) was connected via 2-way adapter connector arm (305) to a 500 ml 3-neck round bottom flask (304) and a 100 ml single neck round bottom flask (hereafter 100 ml flask) (303) .
- the 500 ml 3-neck round bottom flask (304) was fitted with a 250 ml addition funnel (316) and a first inlet (312) with a first stopcock (313) for nitrogen purge.
- the 500 ml 3-neck round bottom flask (304) was set in a 500 ml heating mantle (Glas-Col, model 100B TM106, available from VWR Scientific Products, Willard, Ohio) (not shown) . No Heating Mantle was used for the 100 ml flask.
- the distillation column (300) was wrapped with 4 foot heating tape (Electrothermal® HT6 Series #HT641S962, available from VWR Scientific Products, Willard, Ohio) (not shown) .
- the lower extension of the 2-way adapter vertical leg (306) was wrapped with a second, smaller, 2 foot heating tape (Electrothermal® HT640, available from VWR Scien- tific Products, Willard, Ohio) (not shown) .
- the 2-way adapter connector arm (305) was wrapped with 2 layers of
- Nomex® insulating tape available from VWR Scientific Products, Willard, Ohio (not shown). The top half of the 500 ml 3-neck round bottom flask (304) was wrapped with 2 layers of insulating cloth.
- the 500 ml 3-neck round bottom flask (304) was charged with ⁇ 400 ml of tetradecane (Aldrich Chemical #17,245-6, b.p. 252°C) and -150 ml of tetradecane were charged into the 2-way adapter vertical leg (306) and the 100 ml flask (303) .
- Purge nitrogen was applied to the 500 ml 3-neck round bottom flask (304) through first inlet (312) and first stopcock (313) and to the top of the distillation column (300) through second inlet (314) .
- the 500 ml heating mantle and the 2-foot heating tape on the lower extension of the 2-way adapter vertical leg (306) were heated sufficient to bring the tetradecane to a boil.
- the nitrogen purge to the 500 ml 3-neck round bottom flask (304) was stopped.
- the distillation column (300) was allowed to come to a steady reflux over an ⁇ 1 h time period.
- third arrow (309) and second arrow (308) indi- cate generally the direction of flow of the vapor phase tetradecane in the system, and first arrow (307) and fourth arrow (310) indicate generally the direction of flow of the returning tetradecane condensate in the system.
- heat was applied to the distil- lation column (300) via the heating tape.
- first arrow (307) and fifth arrow (311) indicate generally the direction of flow of the pre-polymer melt through the system.
- hot tetradecane solution was allowed to drain from the 500 ml 3-neck round bottom flask (304) by means of the regulator valve (318) , into the collection flask (315) , at a rate of approximately 1-2 ml/minute.
- Fresh, fil-tered, tetradecane was supplied to the 500 ml 3-neck round bottom flask (304) through the 250 ml addition funnel (316) and second stopcock (317) at a rate of 1-2 ml/min.
- poly (butylene terephthalate) pre-polymer was introduced into the top of the distillation column (300) at the rate of approximately 0.5 g/min. .
- hot tetradecane solution was allowed to drain from the 500 ml 3-neck round bottom flask (304) by means of the regulator valve (318) , into the collection flask (315) , at a rate of approximately 1-2 ml/min.
- Fresh, filtered, tetradecane was supplied to the 500 ml 3-neck round bottom flask (304) through the 250 ml addition funnel (316) at a rate of 1-2 ml/min.
- Experimental Segment E was carried out after completion of Experimental Segment D, as follows.
- the distillation process equipment was reassembled and heat applied in the same order as described in Experimental Segment A' .
- this Experimental Segment E' however, no poly (butylene terephthalate) pre-polymer was added to the top of the distillation column (300) .
- the hot tetradecane solvent was allowed to act on that poly (butylene terephthalate) remaining on the sieve trays (302) of the distillation column (300) .
- hot tetradecane solution was allowed to drain from the 500 ml 3-neck round bottom flask (304) by means of the regulator valve (318) , into the collection flask (315) , at a rate of approximately 1-2 ml/min.
- Fresh, filtered, tetradecane was supplied to the 500 ml 3-neck round bottom flask (304) through the 250 ml addition funnel (316) at a rate of 1-2 ml/min.
- the 1100 LC was attached to two detectors; [1] HP G1315 Diode Array Detector and [2] HP G1946A Mass Spectrometer Detector. It is believed, based on analysis of the LC scans, that all of the precipitate samples contained at least 90%, by weight, CEOs. Typical CEO distributions from PBT were approximately dimer 30%, trimer 40%, tet- ramer 15%, pentamer 10%, others 5% (percentages are mole percents) . TABLE 1
- Example 2.1 poly (1,4- butylene terephthalate) (PBT) Exit Polymer from Example 1 was measured by Liquid Chromatography/Mass Spectrometry analysis and found to contain 0%, by weight, CEO. This compares with a CEO content of 12.48 %, by weight, deter- mined for the linear polybutylene terephthalate pre- polymer feed used in Example 1 (PBT Feed, Table 2 below) .
- EXAMPLE 3 Referring to Figure 3, an Oldershaw, perforated bubble plate, distillation column (28 mm inner diameter, 10 plate sections, available from LabGlass, Vineland, New Jersey, as item #LG-5621-122) (300) having downcomers (301) and sieve trays (302) was connected via 2-way adapter connector arm (305) to a 250 ml 3-neck round bottom flask (304) and a 100 ml single neck round bottom flask (hereafter 100 ml flask) (303) .
- the 250 ml 3-neck round bottom flask (304) was fitted with a 250 ml addition funnel (316) and a first inlet (312) with a first stopcock (313) for nitrogen purge.
- the 250 ml 3-neck round bottom flask (304) was set in a 250 ml heating mantle (Glas-Col® model 100B TM106, available from VWR
- the lower extension of the 2-way adapter vertical leg (306) was wrapped with a second, smaller, 2 foot heating tape (Electrothermal® HT640, available from VWR Scientific Products, Willard, Ohio) (not shown) .
- the 2-way adapter connector arm (305) was wrapped with 2 layers of Nomex® insulating tape (available from VWR Scientific Products, Willard, Ohio) (not shown) .
- the top half of the 250 ml 3-neck round bottom flask (304) was wrapped with 2 layers of insulating cloth.
- the 250 ml 3-neck round bottom flask (304) was charged with -200 ml of Fluorinert® FC-70 (3M Industrial Chemical products Division, St. Paul, MN 55144, b.p.
- first arrow (307) and fifth arrow (311) indicate generally the direction of flow of the pre-polymer melt through the system] .
- hot Fluorinert® FC-70 solution was allowed to drain from the 250 ml 3-neck round bottom flask (304) by means of the regulator valve (318) , into the collection flask (315), at a rate of approximately 1-2 ml/minute.
- Fresh, filtered, Fluorinert® FC-70 was supplied to the 250 ml 3-neck round bottom flask (304) through the 250 ml addition funnel (316) and second stopcock (317) at a rate of 1-2 ml/min. After a running time of 6-8 h, all heat was turned off and the distillation column (300) and the Fluorinert® FC-70 solution was allowed to cool to room temperature overnight. All of the Fluorinert® FC-70 solution was then filtered through a coarse sintered filter.
- Analysis of the CEO was performed using a Hewlett Packard 1100 Liquid Chromatograph fitted with 2 Plgel® 50A chromatography columns. The 1100 LC was attached to two detectors; [1] HP G1315 Diode Array Detector and [2] HP G1946A Mass Spectrometer Detector. It is believed, based on analysis of the LC scans, that all of the precipitate samples contained at least 90%, by weight, CEOs.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002568004A JP4060189B2 (en) | 2001-02-28 | 2002-02-28 | Production of cyclic ester oligomers |
DE60201084T DE60201084T2 (en) | 2001-02-28 | 2002-02-28 | PREPARATION OF CYCLIC ESTEROLIGOMERS |
KR1020037011247A KR100798242B1 (en) | 2001-02-28 | 2002-02-28 | Manufacture of Cyclic Ester Oligomers |
EP02723304A EP1377623B1 (en) | 2001-02-28 | 2002-02-28 | Manufacture of cyclic ester oligomers |
CA002437562A CA2437562A1 (en) | 2001-02-28 | 2002-02-28 | Manufacture of cyclic ester oligomers |
AU2002254092A AU2002254092A1 (en) | 2001-02-28 | 2002-02-28 | Manufacture of cyclic ester oligomers |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US27209401P | 2001-02-28 | 2001-02-28 | |
US27209301P | 2001-02-28 | 2001-02-28 | |
US27209601P | 2001-02-28 | 2001-02-28 | |
US27209501P | 2001-02-28 | 2001-02-28 | |
US60/272,094 | 2001-02-28 | ||
US60/272,095 | 2001-02-28 | ||
US60/272,096 | 2001-02-28 | ||
US60/272,093 | 2001-02-28 | ||
US35161602P | 2002-01-24 | 2002-01-24 | |
US60/351,616 | 2002-01-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002068496A1 true WO2002068496A1 (en) | 2002-09-06 |
WO2002068496A8 WO2002068496A8 (en) | 2003-02-06 |
Family
ID=28795332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/006398 WO2002068496A1 (en) | 2001-02-28 | 2002-02-28 | Manufacture of cyclic ester oligomers |
Country Status (9)
Country | Link |
---|---|
US (1) | US6646134B2 (en) |
EP (1) | EP1377623B1 (en) |
JP (1) | JP4060189B2 (en) |
KR (1) | KR100798242B1 (en) |
CN (1) | CN1269868C (en) |
AU (1) | AU2002254092A1 (en) |
CA (1) | CA2437562A1 (en) |
DE (1) | DE60201084T2 (en) |
WO (1) | WO2002068496A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010101913A1 (en) * | 2009-03-03 | 2010-09-10 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) pellets with reduced oligomers and method to measure oligomer reduction |
US8063169B2 (en) | 2006-05-31 | 2011-11-22 | E. I. Du Pont De Nemours And Company | Preparation of polyamide block copolymers |
US8071677B2 (en) | 2008-12-12 | 2011-12-06 | E. I. Du Pont De Nemours And Company | Process for preparing polyester composite materials |
US9040615B2 (en) | 2004-12-22 | 2015-05-26 | E I Du Pont De Nemours And Company | Compositions of polyesters and fibrous clays |
CN112705150A (en) * | 2020-11-05 | 2021-04-27 | 中国恩菲工程技术有限公司 | Composite material preparation device and method |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
US7071291B2 (en) | 2001-06-27 | 2006-07-04 | Cyclics Corporation | Isolation, formulation and shaping of macrocyclic oligoesters |
TW201534636A (en) * | 2014-02-12 | 2015-09-16 | Invista Tech Sarl | High intrinsic viscosity column reactor for polyethylene terephthalate |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0798336A2 (en) * | 1996-03-20 | 1997-10-01 | General Electric Company | Process for depolymerizing polyesters |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2020298A (en) | 1935-11-12 | Cyclic ester | ||
US5466744A (en) | 1990-11-05 | 1995-11-14 | General Electric Company | Polymerization of macrocyclic poly(alkylene dicarboxylate) oligomers |
US5214158A (en) | 1991-06-03 | 1993-05-25 | General Electric Company | Method for preparation of macrocyclic poly(alkylene dicarboxylate) oligomers |
US5407984A (en) | 1994-08-31 | 1995-04-18 | General Electric Company | Process for preparing macrocyclic polyester oligomers |
US5661214A (en) | 1996-08-05 | 1997-08-26 | General Electric Company | Titanate esters useful as polymerization initiators for macrocylic polyester oligomers |
-
2002
- 2002-02-25 US US10/083,864 patent/US6646134B2/en not_active Expired - Fee Related
- 2002-02-28 KR KR1020037011247A patent/KR100798242B1/en not_active IP Right Cessation
- 2002-02-28 DE DE60201084T patent/DE60201084T2/en not_active Expired - Lifetime
- 2002-02-28 WO PCT/US2002/006398 patent/WO2002068496A1/en active IP Right Grant
- 2002-02-28 JP JP2002568004A patent/JP4060189B2/en not_active Expired - Fee Related
- 2002-02-28 AU AU2002254092A patent/AU2002254092A1/en not_active Abandoned
- 2002-02-28 CN CNB028056817A patent/CN1269868C/en not_active Expired - Fee Related
- 2002-02-28 EP EP02723304A patent/EP1377623B1/en not_active Expired - Lifetime
- 2002-02-28 CA CA002437562A patent/CA2437562A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0798336A2 (en) * | 1996-03-20 | 1997-10-01 | General Electric Company | Process for depolymerizing polyesters |
Non-Patent Citations (1)
Title |
---|
HALL A J ET AL: "Recent research on the synthesis and applications of cyclic oligomers", REACTIVE & FUNCTIONAL POLYMERS, ELSEVIER SCIENCE PUBLISHERS BV, NL, vol. 41, no. 1-3, 15 July 1999 (1999-07-15), pages 133 - 139, XP004172667, ISSN: 1381-5148 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9040615B2 (en) | 2004-12-22 | 2015-05-26 | E I Du Pont De Nemours And Company | Compositions of polyesters and fibrous clays |
US8063169B2 (en) | 2006-05-31 | 2011-11-22 | E. I. Du Pont De Nemours And Company | Preparation of polyamide block copolymers |
US8691894B2 (en) | 2006-05-31 | 2014-04-08 | E I Du Pont De Nemours And Company | Preparation of polyamide block copolymers |
US8071677B2 (en) | 2008-12-12 | 2011-12-06 | E. I. Du Pont De Nemours And Company | Process for preparing polyester composite materials |
WO2010101913A1 (en) * | 2009-03-03 | 2010-09-10 | E. I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) pellets with reduced oligomers and method to measure oligomer reduction |
CN112705150A (en) * | 2020-11-05 | 2021-04-27 | 中国恩菲工程技术有限公司 | Composite material preparation device and method |
Also Published As
Publication number | Publication date |
---|---|
EP1377623A1 (en) | 2004-01-07 |
KR100798242B1 (en) | 2008-01-24 |
CA2437562A1 (en) | 2002-09-06 |
DE60201084D1 (en) | 2004-09-30 |
WO2002068496A8 (en) | 2003-02-06 |
AU2002254092A1 (en) | 2002-09-12 |
JP2004536161A (en) | 2004-12-02 |
CN1269868C (en) | 2006-08-16 |
EP1377623B1 (en) | 2004-08-25 |
US6646134B2 (en) | 2003-11-11 |
KR20030094264A (en) | 2003-12-11 |
DE60201084T2 (en) | 2005-09-29 |
US20030009037A1 (en) | 2003-01-09 |
JP4060189B2 (en) | 2008-03-12 |
CN1494563A (en) | 2004-05-05 |
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